Dimers of 2-methyl-pentadiene and process for preparing same



rammed Jan. 23, 1945 2,368,068

UNITED STATES PATENT OFFICE DlltlERS OF 2-METHYL-PENTADIENE AND PROCESS FOR PREPARING SAME Glen H. Morey, Terre Haute, Ind.,'assignor to Commercial Solvents Corporation, Terre Haute, Ind., a corporation of Maryland No Drawing. Application January 28, 1942, Serial No. 428,576

3 Claims. (Cl. 260-682) The present invention relates to a new and I have produced constitutes such a mixture useful composition of matter. More particularly, isomers. it relates to the dimeric form of 2-methylpenta- The process by which the dimers of the presdiene, and to a process for producing the latter ent invention may be prepared is subject to from 2-methyl-2A-pentanediol. numerous variations. The quantity of mineral It is well .known in the art that numerous acid employed will vary with the method utilized monohydric and polyhydric alcohols may be de--- fin preparing the above-mentioned mixture of hydrated to yield respectively the corresponding I dimers. For example, if. it is.desired to obtain olefines or polyolefines by treating said mono-. said dimers within a short period of time, a soluhydric or polyhydric alcohols with certain. of the tionconsisting of 2-methyl-2,4-pentanediol and mineral acids. In all of such instances, however, from about 2 to 5 per cent by volume of the so far as I am aware, the monomeric form of the mineral acid is heated to refluxing temperature 7 olefine is produced, together, in certain instances, and distilledrthe dimer being Produced pp with varying quantities of the product resulting matelysas rapidly as the distillation proceeds. from the addition of the elementsoi the mineral mp Yields of the dimers 01 y -p acid to the resulting olefine. Thus, for example, them; may be obtained by reacting substantially upon treating tertiary butyl alcohol with concenequal parts-[by volume of 2-methyl-2.4-pentanetrated hydrochloric acid, isobutylene is presumdiol andthemineral acid at room temperature, ably formed, a substantial proportion of which i. e., -30"v C., and permitting the resulting mixsubsequently adds on the elements of hydro- 2o ture to stand for a periodof from 5 to 6 hours. chloric acid to form tertiary butyl chloride- The m n ralacid is completely s u e in resulting mixture is found to consist essentially 2-methyl-2,4-pentanediol, and consequently upon oi tertiary butyl chloride and varyin amounts ixing th se two m t ria s. a l ar-s uti n reot isobutylene, depending upon the conditions i s. However, under ordinary conditions the under which the reaction was efiected. There is 25 reaction mixture, upon standing, becomes prono evidence of extensive polymerization of said g essively t the P t eparatin as a isobutylene occurring, and never under such con-, milky white oil and constituting the upper layer; ditions, to my knowledge, has there ever been rwhereas-the'water produced by the'dehydration detected the dimer of lsobutylene (diisobutylene) reviet onjtosether with t e un eac d ethy in the slightest trace, when hydrochloric .acid is so 2,4-pentanediol, comprise the lower layer. At the used. Itls necessary to use polymerization catacon lusi n of the} reaction, however, he lower lysts to polymerize isobutylene, T y COHSIStS p n ip y f W t he maj P Contrary to what one versed in the art would tionot Z-methyi-ZA-pentanedioI having been denormally expect, in view of the above facts, 'hydrated'upon contact with the mineral acid. have found that by contacting 2-methyl-'2,4+ j Thelipperoil layer m y then be Separated y pentanediol with a suitable mineral acid, such as, r ny convenient means. n the rs ined for example, hydrochloric, sulfuric, or hydr' upon fractionation. i bromic acids, at temperatures ranging from ap- I The examples which follow are illustrative of proximately 10 C. to about 100 0., depending? certain modifications of my novel process. on the method selected, appreciable quantities of 40" Example I the dimeric form of the corresponding dioleilne '(2 m thy] e ntad1ene) are produced together v A solution consisting of 2500 parts 0! Z-methwith 2 methyl-pentene 2 ol- 4, and a mau yl-2,4-pentanediol and 75 parts of concentrated t; of more highly polymerized bst n hydrochloric acid, was heated to refluxing temh product hi h I bt i may b prepared perature and then carefullyfractionated. The either by heating a mixture of the 2- t 4- distillate thus obtained separated into two laypentanediol and a mineral acid to reflux temperersl the upp layer O Which contained the crude store and distilling, or permitting said mixture mixture of dimers oi 2-methylpentadiene, toto stand at a lower temperature, preferably room gether with a sma a ou t o et y p temperature, for a period of from 5 to 6 hours. tadiene and some y D e e- -01-4. It will be evident, from an inspection of the s upper y r was separated and fractionally structural formula of 2-methy1-pentadiene, that distilled under reduced P e su d the D the dimer produced therefrom is, theoretically, at tion boiling at 09 C. (50 mm.) collected sepaleast, capable of existing in several isomeric rately. The quantity oi 2-methylpentadlene terms, and it is believed that the product which dimer Obtained at this temperature. amounted to a yield of 35 per cent based upon the Z-methvl- 2,4-pentanedlol.

Example 11 A solution consisting of 2000 parts of 2-methyl-2,4-pentanediol and 2000 parts of concentrated sulfuric acid was permitted to stand for hours. At the conclusion of this period the oily upper layer was separated and fractionated as described in Example I. The quantity of 2- methylpentadiene dimer, produced in this manner, corresponded to a yield of 55 per cent based upon the 2-methyl-2,4-pentanediol.

The following data were determined on the product produced as described above: boiling point, 109' C.-l12 C. (50 mm); molecular weight, found 168, theory 164; bromine absorption, found 2.5 grams/gram, theory 2.9 grams/gram; carbon analysis, found 86.31, theory 87.8.

It is to be understood that while the properties listed immediately above will be useful in identifying the product of the present invention, I do not desire to be restricted solely to a material having the exact propertie listed, since the number of preparations from which the above data were determined, was limited.

The product of the present invention has been found to be useful in the preparation of various coating compositions, particularly where special solvent properties are desired. Other uses of this material will be apparent to those skilled in the art.

My invention now having been described, what I claim is:

1. A process for the preparation of dimers of 2-methylpentadiene, which comprises contacting 2-methyl-2,4-pentanediol with from about 2 to per cent by volume of a mineral acid selected from the group consisting of hydrochloric, sulfuric, and hydrobromic acids.

2. A process for the preparation of dimers of 2 -methylpentadiene, which comprises distilling 2-methyl-2,4-pentanediol in the presence of ap proximately 2 to 5 per cent by volume of a mineral acid selected from the gorup consisting of hydrochloric, sulfuric, and hydrobromic acids.

3. A process for the preparation of dimers of Z-methylpentadiene, which comprises contacting approximately equal volumes of 2-methyl-2,4- pentanediol and a mineral acid selected from the group consisting of hydrochloric, sulfuric, and hydrobromic'acids.

' GLEN H. MORIY. 

